Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols

ABSTRACT

A process for producing a lower aliphatic carboxylic acid alkenyl, comprising reacting a lower olefin, a lower aliphatic carboxylic acid and oxygen in a gas phase in the presence of a catalyst comprising a support having supported thereon a catalyst component containing a compound containing alkali metal and/or alkaline earth metal, an element belonging to Group 11 of the Periodic Table or a compound containing at least one of these elements, and palladium, wherein the conversion of the lower aliphatic carboxylic acid is 80% or less or the concentration of the lower aliphatic carboxylic acid at the reactor outlet is 0.5 mol % or more.

CROSS-REFERENCE TO RELATED APPLICATION

This application is an application filed under 35 U.S.C. §111(a)claiming benefit pursuant to 35 U.S.C. §119(e)(1) of the filing date ofthe Provisional Application 60/455,588 filed Mar. 19, 2003, pursuant to35 U.S.C. §111(b).

TECHNICAL FIELD

The present invention relates to processes for producing a loweraliphatic carboxylic acid alkenyl and an alkenyl alcohol; and a loweraliphatic carboxylic acid alkenyl and an alkenyl alcohol obtained by theproduction processes. More specifically, the present invention relatesto a process for producing a lower aliphatic carboxylic acid alkenylfrom a lower olefin, a lower aliphatic carboxylic acid and oxygen; alower aliphatic carboxylic acid alkenyl obtained by the productionprocess; a process for producing an alkenyl alcohol by hydrolyzing theabove-described lower aliphatic carboxylic acid alkenyl; and an alkenylalcohol obtained by this production process.

BACKGROUND ART

In the production process of a lower aliphatic carboxylic acid alkenyl,where a lower aliphatic carboxylic acid alkenyl is obtained by a gasphase reaction starting from a lower olefin, a lower aliphaticcarboxylic acid and oxygen, a catalyst comprising a support havingsupported thereon palladium as the main catalyst component and an alkalimetal and/or alkaline earth metal compound as a co-catalyst is widelyused. For example, Japanese Unexamined Patent Publication No. 2-91045(JP-A-2-91045) discloses a process for producing allyl acetate by usinga catalyst comprising a support having supported thereonpalladium/potassium acetate/copper.

In the production of allyl acetate by using this catalyst system, aphenomenon wherein a compound containing alkali metal and/or alkalineearth metal or a component derived from the compound as one component ofthe catalyst (hereinafter, these are collectively called an “alkalicomponent(s)”) desorbs and flows out from the catalyst during thereaction is seen and this is considered to be one cause bringing aboutdeactivation of the catalyst. The mechanism of desorption is notparticularly understood, but one reason for the desorption occurring isbelieved to be that the lower aliphatic carboxylic acid in the startingmaterial and the alkali component(s) react, producing a new compound(hereinafter referred to as a “lower aliphatic carboxylic acidcompound”), and this lower aliphatic carboxylic acid compound is morereadily desorbed from the catalyst than the alkali component(s) presentin the catalyst.

For the purpose of overcoming this problem, in JP-A-2-91045, at theproduction of allyl acetate in the presence of a catalyst comprisingpalladium/potassium acetate/copper, a potassium acetate is added to thesupply gas and mixed into the system so as to compensate for the amountof potassium acetate desorbed from the catalyst. Also, in JapaneseUnexamined Patent Publication No. 61-238759 (JP-A-61-238759), 20 ppm ofpotassium acetate is added to the starting material acetic acid at thetime of producing allyl acetate in the presence of a palladium/potassiumacetate catalyst.

These techniques have a certain effect from the standpoint of preventingthe catalyst from reducing in activity due to flowing out of an alkalimetal and/or alkaline earth metal compound, particularly potassiumacetate at the production of allyl acetate. However, as described inthese patent publications, a highly efficient and industrially stableproduction can sometimes not continue over a long time only by controlof the amount of potassium acetate added to the starting material. Morespecifically, the potassium acetate added is partially deposited in areactor, and as a result, a reaction proceeds locally in a part of thecatalyst layer, reducing the total reaction yield or the catalyst ispartially deteriorated and shortened in its life. Furthermore, thepotassium acetate flowing out from the catalyst is partially deposited,clogging the reaction tube or increasing the flow resistance and it issometimes difficult to carry out the production stably for a long periodof time.

DISCLOSURE OF INVENTION

An object of the present invention is to provide a process capable ofstably producing a lower aliphatic carboxylic acid alkenyl with higherefficiency over a longer period of time.

Another object of the present invention is to provide a process capableof efficiently producing an alkenyl alcohol by hydrolyzing a loweraliphatic carboxylic acid alkenyl produced by the above-describedprocess.

As a result of intensive investigations to attain these objects, thepresent inventors have found that not only by adding an alkalicomponent(s), which flows out, to the starting material and compensatingthe component(s), but also by controlling the outflow of an alkalicomponent(s) contained in the catalyst and adding the component(s) in anamount compensating for the outflow, the activity and life of a catalystcan be maintained and a stable operation can be performed for a longerperiod of time. The present invention has been accomplished based onthis finding.

Specifically, the present invention (I) is a process for producing alower aliphatic carboxylic acid alkenyl, comprising reacting a lowerolefin, a lower aliphatic carboxylic acid and oxygen in a gas phase inthe presence of a catalyst comprising a support having supported thereona catalyst component containing (a) a compound containing alkali metaland/or alkaline earth metal, (b) an element belonging to Group 11 of thePeriodic Table or a compound containing at least one of these elements,and

(c) palladium, wherein the conversion of the lower aliphatic carboxylicacid, represented by formula (1), is 80% or less:Conversion (%)={(amount (mol) of lower aliphatic carboxylic acid atreactor inlet-amount (mol) of lower aliphatic carboxylic acid at reactoroutlet)/amount (mol) of lower aliphatic carboxylic acid at reactorinlet}×100  (1)

The present invention (II) is a lower aliphatic carboxylic acid alkenylproduced by the production process of the present invention (I).

The present invention (III) is a process for producing an alkenylalcohol, comprising hydrolyzing the lower aliphatic carboxylic acidalkenyl of the present invention (II) in the presence of an acidcatalyst to obtain an alkenyl alcohol, and also includes an alkenylalcohol produced by this production process.

The present invention having such constitutions comprises, for example,the following matters.

[1] A process for producing a lower aliphatic carboxylic acid alkenyl,comprising reacting a lower olefin, a lower aliphatic carboxylic acidand oxygen in a gas phase in the presence of a catalyst comprising asupport having supported thereon a catalyst component containing (a) acompound containing alkali metal and/or alkaline earth metal, (b) anelement belonging to Group 11 of the Periodic Table or a compoundcontaining at least one of these elements, and (c) palladium, whereinthe conversion of the lower aliphatic carboxylic acid, represented byformula (1), 80% or less:Conversion (%)={(amount (mol) of lower aliphatic carboxylic acid atreactor inlet-amount (mol) of lower aliphatic carboxylic acid at reactoroutlet)/amount (mol) of lower aliphatic carboxylic acid at reactorinlet}×100  (1)

[2] process for producing a lower aliphatic carboxylic acid alkenyl,comprising reacting a lower olefin, a lower aliphatic carboxylic acidand oxygen in a gas phase in the presence of a catalyst comprising asupport having supported thereon a catalyst component containing (a) acompound containing alkali metal and/or alkaline earth metal, (b) anelement belonging to Group 11 of the Periodic Table or a compoundcontaining at least one of these elements, and (c) palladium, whereinthe concentration of the lower aliphatic carboxylic acid at the reactoroutlet is 0.5 mol % or more.

[3] The production process as described in [1] or [2] above, wherein theoutflow ratio per hour of (a) the compound containing alkali metaland/or alkaline earth metal, represented by formula (2), is from1.0×10⁻⁵ to 0.01%/h:Outflow ratio (%)/h={mass (kg/h) of alkali metal or alkaline earth metaldetected/mass (kg) of alkali metal or alkaline earth metal in the entirecatalyst packed}×100  (2)

[4] The production process as described in any one of [1] to [3] above,wherein (a) the compound containing alkali metal and/or alkaline earthmetal is a compound containing at least one member selected from thegroup consisting of lithium, sodium, potassium, cesium, magnesium,calcium and barium.

[5] The production process as described in any one of [1] to [4] above,wherein (a) the compound containing alkali metal and/or alkaline earthmetal is a salt of a lower aliphatic carboxylic acid.

[6] The production process as described in [5] above, wherein the saltof a lower aliphatic carboxylic acid is at least one member selectedfrom lithium, sodium, potassium, cesium, magnesium, calcium and bariumsalts of formic acid, acetic acid, propionic acid, acrylic acid ormethacrylic acid.

[7] The production process as described in any one of [1] to [6] above,wherein (b) the element belonging to Group 11 of the Periodic Table orthe compound containing at least one of these elements is an element ofcopper or gold or a compound containing one or more of copper and gold.

[8] The production process as described in any one of [1] to [7] above,wherein a lower olefin, a lower aliphatic carboxylic acid and oxygen arereacted in the presence of water.

[9] A lower aliphatic carboxylic acid alkenyl produced by the productionprocess described in any one of [1] to [8] above.

[10] The production process as described in any one of [1] to [8] above,wherein the lower aliphatic carboxylic acid is acetic acid, the lowerolefin is ethylene and the obtained lower aliphatic carboxylic acidalkenyl is vinyl acetate.

[11] Vinyl acetate produced by the production process described in [10]above.

[12] The production process as described in any one of [1] to [8] above,wherein the lower aliphatic carboxylic acid is acetic acid, the lowerolefin is propylene and the obtained lower aliphatic carboxylic acidalkenyl is allyl acetate.

[13] Allyl acetate produced by the production process described in [12]above.

[14] A process for producing an alkenyl alcohol, comprising hydrolyzingthe lower aliphatic carboxylic acid alkenyl described in [9] above inthe presence of an acid catalyst to obtain an alkenyl alcohol.

[15] The production process as described in [14] above, wherein the acidcatalyst is an ion exchange resin.

[16] The production process as described in [14] or

[15] above, wherein the lower aliphatic carboxylic acid alkenyl is allylacetate and the obtained alkenyl alcohol is allyl alcohol.

[17] An alkenyl alcohol produced by the production process described inany one of [14] to [16] above.

[18] Allyl alcohol produced by the production process described in [16]above.

BEST MODE FOR CARRYING OUT THE INVENTION

Preferred embodiments of the present invention are described in detailbelow.

The compound containing alkali metal and/or alkaline earth metal (a) inthe catalyst for use in the present invention (I) is not particularlylimited and examples thereof include compounds containing at least oneof the elements belonging to Groups 1 and 2 of the Periodic Tableaccording to IUPAC Nomenclature of Inorganic Chemistry, Rules 1989. Thiscompound is preferably a compound containing at least one elementselected from the group consisting of lithium, sodium, potassium,cesium, magnesium, calcium and barium, more preferably a salt of a loweraliphatic carboxylic acid, still more preferably at least one memberselected from lithium, sodium, potassium, cesium, magnesium, calcium andbarium salts of formic acid, acetic acid, propionic acid, acrylic acidor methacrylic acid, particularly preferably an acetate, and mostpreferably potassium acetate.

Examples of (b) the element belonging to Group 11 of the Periodic Tableaccording to IUPAC Nomenclature of Inorganic Chemistry, Rules 1989, orthe compound containing at least one of these elements in the catalystfor use in the present invention (I) include Group 11 elements andnitrates, carbonates, sulfates, organic acid salts and halides of aGroup 11 element(s). This component is preferably one or more element(s)selected from copper and gold or a compound thereof, and most preferablycopper alone and/or gold alone.

The palladium (c) in the catalyst for use in the present invention (I)may have any valent number but is preferably metal palladium. The “metalpalladium” as used herein means palladium having 0 valence. Thispalladium can be usually obtained by reducing a divalent and/ortetravalent palladium ion with hydrazine, hydrogen or ethylene as areducing agent. At this time, the palladium need not be entirely in themetal state. The starting material of (c) the palladium is notparticularly limited and metal palladium or a palladium salt capable ofconverting into metal palladium can be used. Examples of the palladiumsalt capable of converting into metal palladium include, but are notlimited to, palladium chloride, sodium chloropalladate, palladiumnitrate and palladium sulfate.

The support used in the catalyst for use in the present invention (I)may be sufficient if it is a commonly employed porous material.Preferred examples thereof include silica, alumina, silica-alumina,kieselguhr, montmorillonite, titania and zirconia, with silica beingmore preferred. The silica as used herein is not limited to SiO₂ butsilica containing impurities may also be used. The shape of the supportis not particularly limited and examples thereof include powder, sphereand pellet, although a spherical support is preferred.

The size of the support used is also not particularly limited and theoptimal size of the support varies, depending on the shape or reactionstyle. For example, when the support is spherical, the particlediameter, which is not particularly limited, is preferably from 1 to 10mm, more preferably from 3 to 8 mm. In the case of performing a reactionby packing the catalyst in a tubular reactor, if the particle diameteris less than 1 mm, a large pressure loss occurs on passing a gas and thegas circulation may not be performed effectively, whereas if theparticle diameter exceeds 10 mm, the reaction gas cannot diffuse intothe inside of catalyst and the catalytic reaction may not proceedeffectively.

As for the pore structure of the support, the average pore diameter ispreferably from 0.1 to 1,000 nm, more preferably from 0.2 to 500 nm, andmost preferably from 0.5 to 200 nm. If the average pore diameter is lessthan 0.1 nm, the gas may hardly diffuse, whereas if it exceeds 1,000 nm,the surface area of the support becomes too small and the catalyticactivity may decrease.

The ratio between support and (c) palladium is, as the mass ratio,preferably support: (c) palladium=10 to 1,000:1, more preferablysupport: (c) palladium=30 to 500:1. If the ratio of support and (c)palladium is, in terms of the mass of support, less than support (c)palladium=10:1, the amount of palladium becomes excessively large forthe support, resulting in a poor palladium dispersion state and thereaction yield may decrease, whereas if the ratio of support and (c)palladium is, in terms of the mass of support, larger than support: (c)palladium=1,000:1, the mass of support becomes too large and this is notpractical.

The ratio among (a) compound containing alkali metal and/or alkalineearth metal, (b) element belonging to Group 11 of the Periodic Table orcompound containing at least one of these elements and (c) palladium is,as the mass ratio, preferably (a) compound containing alkali metaland/or alkaline earth metal: (b) element belonging to Group 11 of thePeriodic Table or compound containing at least one of these elements:(c) palladium=0.1 to 100:0.001 to 10:1, more preferably (a) compoundcontaining alkali metal and/or alkaline earth metal: (b) elementbelonging to Group 11 of the Periodic Table or compound containing atleast one of these elements: (c) palladium=1 to 50:0.05 to 5:1.

The catalyst for use in the present invention (I) can be obtained byloading (a) a compound containing alkali metal and/or alkaline earthmetal, (b) an element belonging to Group 11 of the Periodic Table or acompound containing at least one of these elements and (c) a palladiumon a support. In this case, the method for loading the components (a),(b) and (c) is not particularly limited, but examples thereof include amethod of performing the following steps (1) to (6) in this order:

Step (1):

a step of impregnating a support with an aqueous solution containing asalt of palladium and (b) an element belonging to Group 11 of thePeriodic Table or a compound containing at least one of these elementsto obtain Catalyst Precursor A;

Step (2):

a step of bringing Catalyst Precursor A obtained in the step (1) intocontact with an aqueous solution of an alkali metal salt without dryingthe precursor A to obtain Catalyst Precursor B;

Step (3):

a step of bringing Catalyst Precursor B obtained in the step (2) intocontact with a reducing agent such as hydrazine or formalin to obtainCatalyst Precursor C;

Step (4):

a step of water-washing Catalyst Precursor C obtained in the step (3);

Step (5):

a step of bringing Catalyst Precursor C obtained in the step (4) intocontact with (a) a compound containing alkali metal and/or alkalineearth metal to obtain a catalyst; and

Step (6):

a step of drying the catalyst obtained in the step (5).

The catalyst for use in the present invention (I) is preferably, forexample, a catalyst produced by this method and having a specificsurface area of 10 to 250 m²/g and a pore volume of 0.1 to 1.5 ml/g.

The lower olefin for use in the present invention (I) is notparticularly limited, but is preferably an unsaturated hydrocarbonhaving from 2 to 4 carbon atoms, more preferably ethylene or propylene.The ethylene and propylene are not particularly limited and in thesehydrocarbons, a lower saturated hydrocarbon such as ethane, methane andpropane, or a lower unsaturated hydrocarbon such as butadiene, may bemixed. The hydrocarbon is preferably a high-purity unsaturatedhydrocarbon.

The lower aliphatic carboxylic acid for use in the present invention (I)is not particularly limited, but is preferably a lower aliphaticcarboxylic acid having from 1 to 4 carbon atoms, more preferably formicacid, acetic acid or propionic acid, still more preferably acetic acid.Lower aliphatic carboxylic acids usually available on the market can beused.

The oxygen for use in the present invention (I) is not particularlylimited, and may be supplied in the form of being diluted with an inertgas such as nitrogen or carbon dioxide gas, for example, in the form ofair, but oxygen having a purity of 99% or more is preferably used.

The ratio among lower aliphatic carboxylic acid, lower olefin and oxygenfor use in the present invention (I) is, as the molar ratio, preferablylower aliphatic carboxylic acid:lower olefin:oxygen=1:0.08 to 16:0.01 to4. In the case where the lower olefin is an ethylene, the ratio ispreferably lower aliphatic carboxylic acid:ethylene:oxygen=1:0.2 to9:0.07 to 2, and in the case where the lower olefin is a propylene, theratio is preferably lower aliphatic carboxylic acid:propylene:oxygen=1:1to 12:0.5 to 2.

The reaction starting material gas for use in the present invention (I)contains a lower olefin, a lower aliphatic carboxylic acid and oxygenand, for example, nitrogen, carbon dioxide or rare gas may be used as adiluent, if desired. When the lower olefin, lower aliphatic carboxylicacid and oxygen are denoted as the reaction starting material, the ratioof reaction starting material and diluent is, as the molar ratio,preferably reaction starting material:diluent=1:0.05 to 9, morepreferably reaction starting material diluent=1:0.1 to 3.

The reaction starting material gas for use in the present invention (I)is preferably passed through the catalyst at a space velocity of, in thestandard state, from 10 to 15,000 hr⁻¹, more preferably from 300 to8,000 hr⁻¹. If the space velocity is less than 10 hr⁻¹, the heat ofreaction may be difficult to remove, whereas if the space velocityexceeds 15,000 hr⁻¹, the equipment required, such as a compressor,becomes too large and this is not practical.

In the reaction starting material gas for use in the present invention(I), from 0.5 to 20 mol % of water can be added. Preferably, from 1 to18 mol % of water is added. By virtue of the presence of water in thesystem, although the reasons are not clearly understood, the outflow of(a) the compound containing alkali metal and/or alkaline earth metalfrom the catalyst decreases. Even if water is added in an amountexceeding 20 mol %, the effect is not enhanced, but rather hydrolysis ofan alkenyl acetate may proceed. Therefore, it is preferred that a largeamount of water not be present.

In the production process of the present invention (I), the reaction ofa lower olefin, a lower aliphatic carboxylic acid and oxygen in thepresence of a catalyst may be performed in any conventionally known formas long as it is in a gas phase, but the reaction is preferably afixed-bed flow reaction.

The construction material of the reactor used in performing theproduction process of the present invention (I) is not particularlylimited, but a reactor constituted by a material having corrosionresistance is preferred.

In performing the production process of the present invention (I), thereaction temperature is from 100 to 300° C., preferably from 120 to 250°C. If the reaction temperature is less than 100° C., this maydisadvantageously cause the reaction to proceed at an excessively lowrate, whereas if the reaction temperature exceeds 300° C., the heat ofreaction may not be removed and this is not desirable.

In performing the production process of the present invention (I), thereaction pressure is from 0 to 3 MPaG, preferably from 0.1 to 1.5 MPaG.If the reaction pressure is less than 0 MPaG, this may disadvantageouslycause reduction in the reaction rate, whereas if the reaction pressureexceeds 3 MPaG, the equipment required, such as reaction tube becomesexpensive and this is not practical.

In the present invention (I), the conversion of the lower aliphaticcarboxylic acid is 80% or less. A correlation is present between theconcentration of the lower aliphatic carboxylic acid and the amount of(a) the compound containing alkali metal and/or alkaline earth metaldeposited in the vicinity of the outlet and as the concentration of thelower aliphatic carboxylic acid decreases, the amount of (a) thecompound containing alkali metal and/or alkaline earth metal depositedincreases. If the conversion of the lower aliphatic carboxylic acidexceeds 80%, the concentration of the lower aliphatic carboxylic aciddecreases in the vicinity of the reactor outlet, causing deposition of(a) the compound containing alkali metal and/or alkaline earth metal andthis may result in blockage of reaction or a reduction in catalyticperformance.

Alternatively, in the production process of the present invention (I),the concentration of the lower aliphatic carboxylic acid at the reactoroutlet is 0.5 mol % or more. A correlation is present between theconcentration of the lower aliphatic carboxylic acid and the amount of(a) the compound containing alkali metal and/or alkaline earth metaldeposited in the vicinity of the outlet and as the concentration of thelower aliphatic carboxylic acid decreases, the amount of (a) thecompound containing alkali metal and/or alkaline earth metal depositedincreases. If the concentration of the lower aliphatic carboxylic acidis less than 0.5 mol %, (a) the compound containing alkali metal and/oralkaline earth metal is caused to deposit and this may result inblockage of reaction or a reduction in catalytic performance.

The outflow ratio specified by formula (2), that is, the ratio of thealkali metal and/or alkaline earth metal in the catalyst for use in thepresent invention (I) flowing out from the catalyst, is preferably from1.0×10⁻⁵ to 0.01%/h. If the outflow ratio is less than 1.0×10⁻⁵%/h, thepores of the catalyst may be clogged or the compound containing alkalimetal and/or alkaline earth metal may deposit on the catalyst, causingclogging of the reaction tube, and as a result, the production may notbe stable. On the other hand, if the outflow ratio exceeds 0.01%/h, thecatalytic performance may disadvantageously decrease at a high rate dueto the large outflow of the compound containing alkali metal and/oralkaline earth metal. In this case, the activity may be maintained byfeeding from the reaction inlet a compound containing alkali metaland/or alkaline earth metal in an amount large enough to compensate forthe outflow of the compound containing alkali metal and/or alkalineearth metal, although this is unprofitable.

In formula (2), the mass of alkali metal or alkaline earth metaloutflowing is the mass of alkali metal and/or alkaline earth metalcontained in the gas at the reactor outlet. The alkali metal element oralkaline earth element as used herein indicates the alkali metal elementor alkaline earth metal element contained as a catalyst component in thecatalyst.Outflow ratio (%)/h={mass (kg/h) of alkali metal or alkaline earth metaldetected/mass (kg) of alkali metal or alkaline earth metal in the entirecatalyst packed}×100  (2)

For example, in the production process of allyl acetate, potassiumacetate is generally used as a co-catalyst and the potassium acetate isappropriately added to the reactor even during reaction, because thisco-catalyst flows out from the reaction tube during reaction and iscontained as potassium or a potassium compound in the gas at the reactoroutlet.

The “catalyst packed” as used herein indicates a catalyst packed in thereactor and being in the state before passing a reaction startingmaterial gas. In the case where two or more reactors are present inseries or in parallel in one apparatus (process), the total amount ofcatalyst packed in all reactors is indicated.

The alkali metal element and/or alkaline earth metal element in the gasat the reactor outlet may be detected by any method. Examples thereofinclude a method of detecting the element as a condensate at the time ofseparating and purifying the reactor outlet gas and a method ofadsorbing the element by contacting the reaction mixture with an ionexchange resin or the like. Specific examples thereof include a methodof cooling the reactor outlet gas to an extent of causing condensation,and determining the potassium concentration in the obtained condensateby an analysis method such as induction coupled plasma emissionspectroscopic analysis (hereinafter referred to as “ICP spectroscopicanalysis”) or atomic absorption method. The determination method usingICP spectroscopic analysis is not particularly limited but, for example,an absolute calibration curve method may be used.

In the outflow ratio used in the present invention (I), the mass ofalkali metal or alkaline earth metal in the entire catalyst packedindicates the mass of alkali metal and/or alkaline earth metal in theentire catalyst packed in the reactor, specifically, the mass of alkalimetal and/or alkaline earth metal in the packed catalyst before thecatalyst is used for the reaction. The mass of alkali metal and/oralkaline earth metal in the catalyst changes during reaction due tooutflowing or deposition of the component fed, but the mass of alkalimetal and/or alkaline earth metal as used herein is calculated based onthe catalyst before reaction.

The outflow ratio (%/h) can be controlled by the reaction conditionssuch as reaction temperature, reaction pressure and starting materialcomponent, and the reaction conditions are set to give an outflow ratioin the desired range. The controlling method is not particularly limitedand, for example, the outflow ratio can be increased by elevating thereaction temperature or increasing the ratio of lower aliphaticcarboxylic acid in the starting material component.

During the reaction, (a) a compound containing alkali metal and/oralkaline earth metal must be fed from the reactor inlet in an amountlarge enough to compensate for the mass of the alkali metal and/oralkaline earth metal outflowing. Preferably, alkali metal and/oralkaline earth metal is added as (a) a compound containing alkali metaland/or alkaline earth metal in an amount of 0.01 to 200 mass %, based onthe mass of the alkali metal and/or alkaline earth metal outflowing.More preferably, (a) a compound containing alkali metal and/or alkalineearth metal is added in an amount equivalent to or greater than the massof the alkali metal and/or alkaline earth metal outflowing. Although thereasons are not clearly understood, when (a) a compound containingalkali metal and/or alkaline earth metal is added in an equivalentamount or more, the reaction yield decreases less.

The compound containing alkali metal and/or alkaline earth metal (a) maybe added by any method, but is preferably added by mixing it in areaction starting material gas.

The present invention (II) is described below. The present invention(II) is a lower aliphatic carboxylic acid alkenyl produced by theproduction process of a lower aliphatic carboxylic acid alkenyl of thepresent invention (I). Since halogen is not added to the reactionsystem, the lower aliphatic carboxylic acid alkenyl of the presentinvention (II) is free from mingling of halogen as compared with a loweraliphatic carboxylic acid alkenyl produced by the liquid phase Wackermethod and when used as a starting material, problems such as corrosionof equipment less arise due to no mingling of halogen. Furthermore, whenthis lower aliphatic carboxylic acid alkenyl is used as a startingmaterial, steps such as removal of halogen can be advantageouslydispensed with.

The present invention (III) is described below. The present invention(III) is a process for producing an alkenyl alcohol, comprisinghydrolyzing the lower aliphatic carboxylic acid alkenyl of the presentinvention (II) in the presence of an acid catalyst to obtain an alkenylalcohol, and also includes an alkenyl alcohol produced by thisproduction process.

The lower aliphatic carboxylic acid alkenyl for use in the presentinvention (III) is not particularly limited as long as it is a loweraliphatic carboxylic acid alkenyl obtained by the production process ofthe present invention (I), and may contain impurities. This loweraliphatic carboxylic acid alkenyl is preferably allyl acetate.

The pressure in the hydrolysis reaction is not particularly limited, butthe reaction can be performed, for example, at 0.0 to 1.0 MPaG.

The reaction temperature in the hydrolysis reaction is not particularlylimited, but is preferably from 20 to 300° C., more preferably from 50to 250° C.

The hydrolysis reaction for use in the present invention (III) can beperformed in any reaction system such as gas phase reaction, liquidphase reaction and solid-liquid reaction.

The hydrolysis reaction is preferably performed by adding water to thelower aliphatic carboxylic acid alkenyl so as to elevate the conversionof the lower aliphatic carboxylic acid alkenyl in the hydrolysisreaction. The amount of water added is preferably from 1.0 to 60 mass %,more preferably from 5 to 40 mass %.

Also, the hydrolysis reaction is preferably performed while removing theproduced alkenyl alcohol out of the reaction system. The method forremoving the alkenyl alcohol out of the reaction system is notparticularly limited, but, for example, a method of adding a substancecapable of forming an azeotropic mixture with the alkenyl alcohol andremoving the alkenyl alcohol while performing distillation during thereaction, may be used.

Examples of the acid catalyst for use in the hydrolysis reaction of thelower aliphatic carboxylic acid alkenyl include organic acids, inorganicacids, solid acids and salts thereof. Specific examples thereof includeformic acid, acetic acid, propionic acid, tartaric acid, oxalic acid,butyric acid, terephthalic acid, fumaric acid, heteropolyacid,hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,hydrobromic acid, hydrofluoric acid, silica alumina, silica titania,silica magnesia, acidic cation exchange resin and sodium salt, potassiumsalt, magnesium salt and aluminum salt thereof. Among these, solidacidic cation exchange resin is most preferred in view of easyseparation from the alkenyl alcohol after reaction or acidity. Thisresin is more preferably, for example, an ion exchange resin where anacidic active functional group such as sulfonic acid group is bonded tothe styrene divinylbenzene resin skeleton.

The apparatus of performing the hydrolysis reaction for use in thepresent invention (III) is not particularly limited, but a fixed bedflow-type reactor is preferred. When two or more reactor units are usedin parallel, a constant amount of an alkenyl alcohol can be continuouslyobtained, and therefore this is preferred.

In the present invention (III), the method of producing an alcohol in afixed bed flow-type reactor by using an acidic cation exchange resin asthe hydrolysis catalyst is not particularly limited, but a method ofcausing an ascending flow to convey a reaction solution containing thelower aliphatic carboxylic acid alkenyl and water from the bottom of thereactor into the reactor system is preferred. In this case, thecoagulation of ion exchange resin and the drifting of reaction startingmaterial, which may occur in the case of passing the reaction solutionfrom the top to the bottom, can be suppressed.

The alkenyl alcohol of the present invention (III) is described below.This alcohol is advantageously free from mingling of halogen, becausethe lower aliphatic carboxylic acid alkenyl as the starting materialdoes not contain halogen. Therefore, when this alcohol is used as astarting material, steps such as removal of halogen, giving rise tocorrosion of equipment, can be dispensed with and the process can beadvantageously simplified.

The present invention is described in greater detail below by referringto Examples. However, the present invention is not limited thereto.

The reactor outlet gas was analyzed by the following methods.

1. Propylene

An absolute calibration curve method was employed for analysis, where 50ml of the outflow gas was sampled and the entire amount of the gasflowed into a 1-ml gas sampler attached to a gas chromatograph and wasanalyzed under the following conditions.

Gas Chromatography:

-   -   gas chromatograph (GC-7B manufactured by Shimadzu Corporation)        with a gas sampler (MGS-4, measuring tube: 1 ml) for Shimadzu        Gas Chromatograph        Column: packed column Unibeads IS, length: 3 m        Carrier gas: helium (flow rate: 35 ml/min)        Temperature Conditions:    -   The detector temperature was 100° C., the vaporization chamber        temperature was 140° C. and the column temperature was        constantly 140° C.        Detector: TCD (He pressure: 125 kPaG, current: 125 mA)

2. Oxygen

An absolute calibration curve method was employed for analysis, where 50ml of the outflow gas was sampled and the entire amount of the gasflowed into a 1-ml gas sampler attached to a gas chromatograph and wasanalyzed under the following conditions.

Gas Chromatography:

-   -   gas chromatograph (GC-14B manufactured by Shimadzu Corporation)        with a gas sampler (MGS-4, measuring tube: 1 ml) for Shimadzu        Gas Chromatograph        Column: MS-5A IS, 60/80 mesh (3 mmφ×3 m)        Carrier gas: helium (flow rate: 20 ml/min)        Temperature Conditions:    -   The temperature of detector and vaporization chamber was 110° C.        and the column temperature was constantly 70° C.        Detector: TCD (He pressure: 70 kPaG, current: 100 mA)

3. Acetic Acid

An internal standard method was employed for analysis, where 1 ml of1,4-dioxane was added as the internal standard to 10 ml of the reactionsolution and 0.2 μl of the resulting analysis solution was injected andanalyzed under the following conditions.

Gas Chromatography:

GC-14B manufactured by Shimadzu Corporation

Column: packed column Thermon 3000 (length: 3 m, inner diameter: 0.3 mm)

Carrier gas: nitrogen (flow rate: 20 ml/min)

Temperature Conditions:

-   -   The temperature of detector and vaporization chamber was 180° C.        and the column temperature was kept at 50° C. for 6 minutes from        the start of analysis, then elevated to 150° C. at a temperature        rising rate of 10° C./min and kept at 150° C. for 10 minutes.        Detector: FID (H₂ pressure: 40 kPaG, air pressure:

100 kPaG)

4. Allyl Acetate

An internal standard method was employed for analysis, where 1 g ofpentyl acetate was added as the internal standard to 25 g of thereaction solution and 0.3 μl of the resulting analysis solution wasinjected and analyzed under the following conditions.

Gas Chromatography:

GC-9A manufactured by Shimadzu Corporation

Column: capillary column TC-WAX (length: 30 m, inner diameter: 0.25 mm,film thickness: 0.5 nm)

Carrier gas: nitrogen (flow rate: 30 ml/min)

Temperature Conditions:

-   -   The temperature of detector and vaporization chamber was 200° C.        and the column temperature was kept at 45° C. for 2 minutes from        the start of analysis, then elevated to 130° C. at a temperature        rising rate of 4° C./min, kept at 130° C. for 15 minutes, again        elevated to 200° C. at a temperature rising rate of 25° C./min        and kept at 200° C. for 10 minutes.        Detector: FID (H₂ pressure: 60 kPaG, air pressure: 100 kPaG)

5. Allyl Alcohol

An internal standard method was employed for analysis, where 200 μl ofn-amine acetate was added as the internal standard to 10 ml of thereaction solution and 0.1 μl of the resulting analysis solution wasinjected and analyzed under the following conditions.

Gas Chromatography:

GC-14B manufactured by Shimadzu Corporation

Column: packed column Thermon 3000 (length: 3 m, inner diameter: 0.3 mm)

Carrier gas: nitrogen (flow rate: 2.0 ml/min)

Temperature Conditions:

-   -   The temperature of detector and vaporization chamber was 180° C.        and the column temperature was kept at 45° C. for 5 minutes from        the start of analysis, then elevated to 130° C. at a temperature        rising rate of 7° C./min and kept at 130° C. for 13 minutes.        Detector: FID (H₂ pressure: 98 kPaG, air pressure: 98 kPaG)        6. Vinyl Acetate

An internal standard method was employed for analysis, where 1 g ofn-propyl acetate was added as the internal standard to 6 g of thereaction solution and 0.3 μl of the resulting analysis solution wasinjected and analyzed under the following conditions.

Gas Chromatography:

GC-9A manufactured by Shimadzu Corporation

-   Column: capillary column TC-WAX (length: 30 m, inner    diameter: 0.25 mm, film thickness: 0.5 μm)    Carrier gas: nitrogen (flow rate: 30 ml/min)    Temperature Conditions:    -   The temperature of detector and vaporization chamber was 200° C.        and the column temperature was kept at 45° C. for 2 minutes from        the start of analysis, then elevated to 130° C. at a temperature        rising rate of 4° C./min, kept at 130° C. for 15 minutes, again        elevated to 200° C. at a temperature rising rate of 25° C./min        and kept at 200° C. for 10 minutes.        Detector: FID (H₂ pressure: 60 kPaG, air pressure: 100 kPaG)

EXAMPLE 1

Preparation of Catalyst A:

Sodium chloropalladate crystal (56.4 mmol), 8.50 mmol of cupric chloridedihydrate and 18.4 mmol of zinc chloride were dissolved in pure waterand the resulting solution was measured to 97% of the water absorptionamount of the support.

The aqueous metal salt solution obtained above was uniformly impregnatedinto a silica support (KA-160 produced by Sud-chemi AG) which waspreviously dried at 110° C. for 4 hours.

Subsequently, sodium metasilicate nonahydrate was dissolved in purewater and the amount of the solution was adjusted to 2 times the waterabsorption amount of the support. The resulting solution was added tothe impregnated support and left standing at room temperature for 20hours to obtain a catalyst.

To this solution, 720 mmol of hydrazine monohydrate was further addedand after stirring at room temperature for 4 hours, the catalyst waswashed with pure water and dried by a hot air dryer at 110° C. for 4hours.

Thereafter, 509 mmol of potassium acetate was dissolved in pure waterand the resulting solution was measured to about 97% of the waterabsorption amount of the catalyst. This solution was uniformly loaded onthe catalyst and then dried at 110° C. for 4 hours to obtain Catalyst Afor reaction.

Reaction:

The obtained catalyst (20 ml) was packed in a stainless steel reactiontube having an inner diameter of 21.4 mm and by supplying a mixed gascontaining 30 mol % of propylene, 7.0 mol % of oxygen, 5.5 mol % ofacetic acid, 14.0 mol % of water and 43.5 mol % of nitrogen, thereaction was performed at a reaction temperature of 135° C. and apressure of 0.8 MPaG. The results are shown in Table 2. Theconcentration of each component in the reaction solution was measured byusing a gas chromatography analyzer. The conversion of acetic acid wascalculated according to formula (1) and the outflow ratio (%/h) wascalculated according to formula (2) from the weight of potassium in thecondensate obtained by cooling the gas at the outlet of the reactiontube and the weight of potassium in the catalyst before use.

Analysis of Potassium:

1. Analysis of Catalyst Before Use

The catalyst before use was finely ground in an agate mortar and thendried at 110° C. for 2 hours to prepare a powder sample. To 1 g of thepowder sample, 100 ml of pure water was added and 10 ml of 35%hydrochloric acid was further added. Thereafter, the sample was boiledin a sand bath for 2 hours and then allowed to cool and thereto, purewater was added to a quantity of 500 ml. After filtering, the filtratewas subjected to ICP spectroscopic analysis under the followingconditions by using SPS1700HUR manufactured by Seiko Instruments Inc.and the amount of potassium was calculated.

Measuring method: absolute calibration curve method

Photometric height: 15 nm

High-frequency output: 1.3 kw

Carrier pressure: 0.22 MPa

Plasma flow rate: 16 L/min

Photomultiplier voltage: H

Auxiliary flow rate: 0.5 L/min

2. Analysis of Potassium Detected After Reactor Outlet

The condensate obtained by recovering the reaction gas at normaltemperature and atmospheric pressure was subjected to ICP spectroscopicanalysis under the same conditions as in “1. Analysis of Catalyst BeforeUse” above and the amount of potassium was calculated.

The results are shown in Table 2.

EXAMPLE 2

The reaction was performed in the same manner as in Example 1, exceptthat the reaction conditions were changed as shown in Table 1 to give anacetic acid conversion of 78%. The results are shown in Table 2.

EXAMPLE 3

The reaction was performed in the same manner as in Example 1 whilefeeding potassium acetate in an amount corresponding to the outflowratio (%/h), from the reaction tube inlet during reaction. The resultsare shown in Table 2.

EXAMPLE 4

Preparation of Catalyst B:

An aqueous solution containing 47.0 mmol of sodium chloropalladate and10.2 mol of chloroauric acid tetra-hydrate was dissolved in pure waterand the resulting solution was measured to 90% of the water absorptionamount of the support.

The aqueous metal salt solution obtained above was uniformly impregnatedinto a silica support (KA-160) which was previously dried at 110° C. for4 hours.

Subsequently, 135 mmol of sodium metasilicate nonahydrate was dissolvedin pure water and the amount of the solution was adjusted to 2 times thewater absorption amount of the support. The resulting solution was addedto the impregnated support and left standing at room temperature for 20hours to obtain a catalyst.

To this solution, 538 mmol of hydrazine monohydrate was further addedand after stirring at room temperature for 4 hours, the catalyst waswashed with pure water and dried by a hot air dryer at 110° C. for 4hours.

Thereafter, 33 g of potassium acetate was dissolved in pure water andthe resulting solution was measured to about 90% of the water absorptionamount of the catalyst. This solution was uniformly loaded on thecatalyst and then dried at 110° C. for 4 hours to obtain Catalyst B forreaction.

Then, the reaction was performed in the same manner as in Example 1,except that the reaction conditions were changed as shown in Table 1.Also, the analysis was performed in the same manner as in Example 1.

COMPARATIVE EXAMPLE 1

The reaction was performed at a reaction temperature of 165° C. using astarting material having a propylene concentration of 25 mol %, anacetic acid concentration of 2.5 mol %, a water concentration of 25 mol% and a nitrogen concentration of 39.5 mol %. The results are shown inTable 2. After the reaction, the catalyst was drawn out, and as aresult, potassium acetate was found to be present in the vicinity of thereaction tube outlet. The reduction ratio of STY was large. TABLE 1Reaction Reaction Reaction Gas SV Temperature Pressure Olefin OxygenAcetic Acid Water Nitrogen Catalyst h⁻¹ ° C. MPaG mol % Example 1 A 1600135 0.8 propylene 30 7 5.5 14 43.5 Example 2 A 1600 145 0.8 propylene 306.5 5 14 44.5 Example 3 A 1600 135 0.8 propylene 30 7 5.5 14 43.5Example 4 B 2700 150 0.8 ethylene 60 6.5 17 1.3 15.2 Comparative A 1600165 0.8 propylene 25 8 2.5 25 39.5 Example 1

TABLE 2 Alkenyl Alkeriyl Acetate, Concentration Acetate, STY SelConversion of Acetic after after after after of Acetic Acid Acid atOutlet 5 h 2400 h 5 h 2400 h after 5 h after 5 h Outflow Ratio g/L-cat %% mol % %/h Example 1 355.7 291.7 92 91 70.3 2.34 6.5 × 10⁻⁴ Example 2366.6 300.6 94 90 78 1.61 0.008 Example 3 355.7 320.1 92 91 70.3 2.346.5 × 10⁻⁴ Example 4 349.7 301.4 92 90 26 16.3 2.2 × 10⁻⁴ Comparative213.9 160.4 93 42 92 0.43   8 × 10⁻⁵ Example 1

INDUSTRIAL APPLICABILITY

According to the present invention, in producing a lower aliphaticcarboxylic acid alkenyl from a lower aliphatic carboxylic acid, a lowerolefin and oxygen, the compound containing alkali metal and/or alkalineearth metal as a catalyst component is controlled in the outflowingduring reaction, so that production can proceed stably for a long timewithout impairing the catalytic activity.

1. A process for producing a lower aliphatic carboxylic acid alkenyl,comprising reacting a lower olefin, a lower aliphatic carboxylic acidand oxygen in a gas phase in the presence of a catalyst comprising asupport having supported thereon a catalyst component containing (a) acompound containing alkali metal and/or alkaline earth metal, (b) anelement belonging to Group 11 of the Periodic Table or a compoundcontaining at least one of these elements, and (c) palladium, whereinthe conversion of the lower aliphatic carboxylic acid, represented byformula (1), 80% or less:Conversion (%)={(amount (mol) of lower aliphatic carboxylic acid atreactor inlet-amount (mol) of lower aliphatic carboxylic acid at reactoroutlet)/amount (mol) of lower aliphatic carboxylic acid at reactorinlet}×100  (1)
 2. A process for producing a lower aliphatic carboxylicacid alkenyl, comprising reacting a lower olefin, a lower aliphaticcarboxylic acid and oxygen in a gas phase in the presence of a catalystcomprising a support having supported thereon a catalyst componentcontaining (a) a compound containing alkali metal and/or alkaline earthmetal, (b) an element belonging to Group 11 of the Periodic Table or acompound containing at least one of these elements, and (c) palladium,wherein the concentration of the lower aliphatic carboxylic acid at thereactor outlet is 0.5 mol % or more.
 3. The production process asclaimed in claim 1 or 2, wherein the outflow ratio per hour of (a) thecompound containing alkali metal and/or alkaline earth metal,represented by formula (2), is from 1.0×10⁻⁵ to 0.01%/h:Outflow ratio (%)/h={mass (kg/h) of alkali metal or alkaline earth metaldetected/mass (kg) of alkali metal or alkaline earth metal in the entirecatalyst packed}×100  (2)
 4. The production process as claimed in anyone of claims 1 to 3, wherein (a) the compound containing alkali metaland/or alkaline earth metal is a compound containing at least one memberselected from the group consisting of lithium, sodium, potassium,cesium, magnesium, calcium and barium.
 5. The production process asclaimed in any one of claims 1 to 4, wherein (a) the compound containingalkali metal and/or alkaline earth metal is a salt of a lower aliphaticcarboxylic acid.
 6. The production process as claimed in claim 5,wherein the salt of a lower aliphatic carboxylic acid is at least onemember selected from lithium, sodium, potassium, cesium, magnesium,calcium and barium salts of formic acid, acetic acid, propionic acid,acrylic acid or methacrylic acid.
 7. The production process as claimedin any one of claims 1 to 6, wherein (b) the element belonging to Group11 of the Periodic Table or the compound containing at least one ofthese elements is an element of copper or gold or a compound containingone or more of copper and gold.
 8. The production process as claimed inany one of claims 1 to 7, wherein a lower olefin, a lower aliphaticcarboxylic acid and oxygen are reacted in the presence of water.
 9. Alower aliphatic carboxylic acid alkenyl produced by the productionprocess as set forth in any one of claims 1 to
 8. 10. The productionprocess as claimed in any one of claims 1 to 8, wherein the loweraliphatic carboxylic acid is acetic acid, the lower olefin is ethyleneand the obtained lower aliphatic carboxylic acid alkenyl is vinylacetate.
 11. Vinyl acetate produced by the production process as setforth in claim
 10. 12. The production process as claimed in any one ofclaims 1 to 8, wherein the lower aliphatic carboxylic acid is aceticacid, the lower olefin is propylene and the obtained lower aliphaticcarboxylic acid alkenyl is allyl acetate.
 13. Allyl acetate produced bythe production process as set forth in claim
 12. 14. A process forproducing an alkenyl alcohol, comprising hydrolyzing the lower aliphaticcarboxylic acid alkenyl as set forth in claim 9 in the presence of anacid catalyst to obtain an alkenyl alcohol.
 15. The production processas claimed in claim 14, wherein the acid catalyst is an ion exchangeresin.
 16. The production process as claimed in claim 14 or 15, whereinthe lower aliphatic carboxylic acid alkenyl is allyl acetate and theobtained alkenyl alcohol is allyl alcohol.
 17. An alkenyl alcoholproduced by the production process as set forth in any one of claims 14to
 16. 18. Allyl alcohol produced by the production process as set forthin claim 16.